KR100721055B1 - Fabrication Method for p-Type Zinc Oxide Thin Films by Atomic Layer Deposition - Google Patents

Abstract

The present invention relates to a method for producing a p-type zinc oxide thin film by the atomic layer deposition method, and more particularly, an atom prepared by alternately supplying a zinc source, an oxygen source, and a dopant source to form a zinc oxide thin film, and heat-treating the same. A p-type zinc oxide thin film is manufactured by a layer deposition method. The p-type zinc oxide thin film according to the present invention has excellent optical, structural, and electrical properties, and is commercialized for mass production of light emitting devices such as light emitting diodes and laser diodes. It can provide useful effects that can be accelerated.

Atomic layer deposition, light emitting diodes, laser diodes, zinc oxide thin films

Description

Fabrication Method for p-Type Zinc Oxide Thin Films by Atomic Layer Deposition

1 illustrates a per cycle source supply sequence in accordance with one embodiment of the present invention;

2 is a graph showing the electrical characteristics of the ZnO thin film after ammonia doping according to an embodiment of the present invention; And

Figure 3 is a schematic diagram of an atomic model showing the effect of the ammonia doping and post-heat treatment according to an embodiment of the present invention.

The present invention relates to a method for manufacturing a p-type zinc oxide thin film by atomic layer deposition, and more particularly, to supply a zinc source, an oxygen source and a dopant source alternately to form a zinc oxide thin film, and optically produced by heat treatment The present invention relates to a p-type zinc oxide thin film having excellent structural and electrical properties.

Zinc Oxide (ZnO) is a material that has been studied for many decades because of its excellent optical, electrical and piezoelectric properties. It is highly applicable to surface acoustic devices, transparent electrodes and optical devices.

In particular, ZnO has a wide band gap of 3.37 eV, and the band gap can be changed to 4 eV by the addition of Mg. Therefore, ZnO attracts attention as a next-generation optical device material capable of generating a laser in the ultraviolet region. I am getting it.

Although the research on the optical device for GaN-based group III nitride has been actively conducted, it has reached the application stage. However, most GaN-based nitride films require a high temperature of 1000 ° C or higher to grow, thus limiting substrate selection. As a result, it is difficult to grow a good quality epitaxial film on a silicon substrate which is most used in a real process.

On the other hand, ZnO has an advantage that the exciton binding energy (exiton binding energy) is 60 meV at room temperature, which is considerably larger than 28 meV of GaN, thereby maximizing the efficiency of an optical device capable of operating at room temperature and high temperature. In addition, since ZnO is capable of growing a high quality epi thin film at a relatively low temperature of about 500 ° C., ZnO has an advantage of easy epitaxial growth over GaN even on a silicon substrate, and thus is in an advantageous position for practical use.

Due to these material advantages, many studies have been conducted to obtain high quality ZnO epitaxial films since the 1990s. Most of the initial research on ZnO thin films has been conducted for the application to transparent electrode devices that can replace ITO (Indium-Tin-Oxide), and the deposition process also uses the sputtering process. Was not quite good. Since then, with the activation of GaN-based optical device research and development, research to obtain high quality epi thin films has begun.

The biggest problem in the practical application of ZnO-based optical devices is that it is difficult to produce a p-type ZnO thin film because an undoped ZnO thin film has an n-type property. Iwata et al. Reported that p-type thin film was manufactured by adding nitrogen when ZnO thin film was grown, but conversion to p-type was not observed. Until now, p-type doping of ZnO has been difficult.

High-quality single crystals are required for application to optical devices such as lasers. However, ZnO is inevitably heterogeneous epitaxial growth since bulk single crystals are not easy to date. However, due to the large difference in lattice constant from most substrate materials (silicon, sapphire, etc.), the grown thin films have many defects, and they have to be minimized since they have a great adverse effect on mineral properties.

In addition, ZnO thin films generally exhibit n-type electrical conductivity due to Zn interstitial atoms or oxygen vacancies. Research on the effect of point defects on the material itself, interfacial defects caused by lattice mismatches, and the effect of oxygen ions in the plasma is insufficient.

In addition, ZnO thin films used as optical materials require high quality crystallinity and uniformity. To meet these demands, Molecular Beam Epitaxy (MBE), Pulsed Laser Deposition (PLD), Chemical Vapor Deposition (CVD), Metal Organic CVD (MOCVD) ), And metal-organic molecular beam epitaxy (MOMBE) and sputtering have recently been used. Among them, the MOCVD method has been widely used for mass production of ZnO thin films.

However, until now, research on the production of ZnO thin films by atomic layer deposition (ALD) has been limited.

Atomic Layer Depostion (ALD) is a technology that is being actively researched as the development of nanoscale semiconductors having a circuit line width of 100 nm or less in earnest. ALD is an advanced technology for forming thin films on an atomic layer basis, and is attracting attention as an essential deposition technology for nanoscale semiconductor manufacturing because it enables ultra-thin film deposition with excellent uniformity.

ALD is a self-limiting film deposition technique that alternately supplies the reactants to adsorb one atomic layer on the substrate. It has several advantages of being able to deposit uniformly over the area. In addition, the thin film has excellent characteristics even at low deposition temperatures, and has a number of advantages such as showing a nearly 100% coverage even in trenches or holes having a high step height, and thus, it is evaluated as the most suitable deposition technique for manufacturing nanoscale semiconductors.

Korean Patent Laid-Open Publication No. 2003-11399 (February 11, 2003) discloses an atomic layer deposition technique (PEALD; Plasma-Enhanced ALD) using plasma, and the Korean Patent No. 496265 (June 10, 2005) discloses an atomic layer deposition method ( ALD) and plasma-applied atomic layer deposition (PEALD) are alternately formed to form a thin film, and the ratio is controlled to predict and control physical properties such as deposition rate, density and related refractive index, dielectric constant, and electrical resistance of the thin film. Many films, such as a thin film formation of the semiconductor element and its control method, are disclosed.

However, to date, the only report is that a boron-doped n-type ZnO thin film was grown on a glass substrate in order to use the ZnO thin film as a transparent conductive film by the ALD method, and a nitrogen-doped p was grown by the ALD method. There is no example of manufacturing a zinc oxide semiconductor thin film.

Accordingly, the present inventors are intensively researching to produce a p-type zinc oxide thin film useful for mass production of light emitting devices, and by forming an n-type zinc oxide thin film by atomic layer deposition, heat treatment is performed to increase the hole concentration. The present invention has been completed by discovering that a p-type zinc oxide thin film having excellent photoluminescence properties such as high quality optical, structural and electrical properties can be manufactured.

Accordingly, the present invention provides a p-type zinc oxide thin film by the atomic layer deposition method which can control the deposition thickness and enables uniform deposition over a large area, not only excellent coverage but also high quality crystallinity, electrical and optical properties. Its purpose is to provide a method for producing a.

The present invention to achieve the above technical problem, (A) growing a zinc oxide thin film by atomic layer deposition; And (b) performing post-heat treatment in an oxygen atmosphere to produce holes in the zinc oxide thin film.

Hereinafter, the present invention will be described in detail.

In step (a), a zinc oxide thin film is grown by atomic layer deposition.

The zinc oxide thin film forming process according to the present invention employs an atomic layer deposition method having extremely high step coverage with strict doping concentration controllability instead of chemical vapor deposition (CVD).

Atomic Layer Deposition (ALD) is a method of depositing a thin film by alternately supplying reactive gases such as a zinc source and an oxygen source to a reactor. By depositing the zinc-containing species, the oxygen-containing species and the dopants on the substrate in different order of injection of the oxygen source and the dopant, one cycle is completed and the zinc oxide thin film layer of the first layer is formed.

Accordingly, the step of forming the p-type zinc oxide thin film according to the ALD of the present invention is preferably,

a) supplying a zinc source to deposit zinc containing species on the substrate;

b) supplying an oxygen source to deposit an oxygen containing species;

c) supplying a nitrogen source as a dopant source to dope the nitrogen containing species; And

d) post-heat treatment in an oxygen atmosphere to generate holes.

In the present invention, the deposition step of the zinc oxide thin film according to the ALD is preferably,

a ') supplying a zinc source to the reactor to deposit zinc containing species on the substrate;

b ') a first purification step of removing unreacted zinc sources and reaction byproducts;

c ') supplying an oxygen source to the reactor to deposit oxygen containing species on the substrate on which the zinc containing species are deposited;

d ') a second purge step of removing unreacted oxygen sources and reaction byproducts;

e ') supplying a nitrogen source as a dopant to the reactor to dope the nitrogen containing species onto the substrate on which the oxygen containing species are deposited; And

f ') a third purge step that removes unreacted nitrogen sources and reaction byproducts.

Also optionally, the depositing of the zinc oxide thin film according to the ALD is:

a '') supplying a zinc source to deposit zinc containing species on the substrate;

b '') a first purification step of removing unreacted zinc sources and reaction byproducts;

c '') supplying a nitrogen source as a dopant source to dope the nitrogen containing species onto the substrate on which the zinc containing species are deposited;

d '') a second purge step of removing unreacted nitrogen sources and reaction byproducts;

e '') supplying an oxygen source to deposit oxygen containing species on the nitrogen doped substrate; And

f '') a third purge step that removes unreacted oxygen sources and reaction byproducts.

In each purification step, when a purge gas is introduced and then a reaction gas is introduced again, the reaction gas is reacted with a previous reactant adsorbed on the substrate to form a thin film. In this case, steps a) to c), preferably a ') to f') or a '') to f '') may be repeatedly performed several times until a zinc oxide film having a desired target thickness is formed. have.

As shown in FIG. 1 , three pulses form a zinc oxide thin film in one cycle. By adjusting the number of cycles, the thickness of the thin film can be controlled very precisely, and the doping concentration can be controlled very precisely by adjusting the number of cycles of the introducing material.

In the purifying step, the excess unreacted gas and reaction by-products are removed by a purge gas, and when the reactant gas is introduced again after the purge gas is introduced, it reacts with the previous reactant adsorbed on the substrate to give a thin film. Will form sugar. Thin film deposition is performed in a surface reaction limiting state while the layers deposited per cycle.

In the present invention, the source of zinc of the zinc-containing species is not particularly limited, but is preferably zinc chloride (ZnCl ₂ ), dimethylzinc (Me ₂ Zn), diethylzinc (Et ₂ Zn). ), Zinc acetate (Zn (CH ₃ COO) ₂ ), and the like, and more preferably dimethylzinc can be used. The use of dimethylzinc as a zinc source enables the use of a substrate having a low melting point, thus keeping the process temperature relatively low, reducing the risk of reactor corrosion and increasing the growth of zinc oxide single crystals. Because it can.

In the present invention, the oxygen source that is the source of the oxygen-containing species is not particularly limited, but preferably, high purity water or oxygen gas may be used, and more preferably high purity water may be used.

In the present invention, as the dopant source for preparing the p-type zinc oxide thin film, nitrogen-containing species such as N ₂ O, NO ₂ or ammonia (NH ₃ ) may be used, but preferably, ammonia is used at a flow rate of 1 to 10 sccm. N-doped zinc oxide thin films may be grown by implantation.

In the present invention, a zinc oxide thin film having improved uniformity and covering property of thin film crystals can be obtained by using dimethyl zinc as the zinc source, water as the oxygen source, and ammonia as the dopant source, respectively. have.

As a board | substrate used for this invention, a conventional thing can be used and a sapphire, a silicon, a glass substrate, etc. can be used typically.

In the present invention, the substrate temperature must be set significantly to form a zinc oxide thin film having excellent film properties and no interface problems by the above-described atomic layer deposition method. For this purpose, the vapor pressure of the deposition gas must be kept constant, and the pressure of the preferred reactor according to the present invention should be maintained at 1 to 10 torr. If the pressure of the reactor is lower than 1 torr, there is a problem that the reaction rate is slow.

In the pressure range, the holding temperature of the substrate according to the present invention is preferably in the range of 110 ° C to 220 ° C, more preferably in the range of 150 ° C to 180 ° C. At this time, if the holding temperature of the substrate is lower than 110 ℃ does not form a crystalline film due to the lack of energy required for the reaction, there is a problem that the quality is lowered due to excessive deposition of zinc at a temperature higher than 220 ℃.

In the present invention, the doping concentration can be controlled very precisely by adjusting the pulse time injected per cycle of the ion source to be adsorbed. To this end, the pulse time of the zinc source of step a) is 0.1 to 0.2 seconds per cycle, the pulse time of the nitrogen source of step c) is 0.01 to 0.1 seconds per cycle and the pulse time of the oxygen source of step e) is cycles It is preferably maintained for 0.1 to 0.3 seconds per sugar.

In the present invention, the unreacted material and reaction by-products can be removed by supplying and purifying vacuum inert gas or inert gas containing argon gas.

Subsequently, in step (b), a cycle having the steps a) to c) as described above, preferably a ') to f') or a '') to f ''), is carried out several times to obtain a desired target thickness. The thin film grown up to is post-heated in an oxygen atmosphere to remove hydrogen of NH or NH _X , which is generated per cycle, or NH ₂ , and NH _{3. The} p-type zinc oxide thin film is formed by forming holes by leaving only nitrogen atoms.

In the present invention, the preferred heat treatment temperature for sufficiently increasing the concentration of nitrogen is 800 ℃ to 1000 ℃. If the heat treatment temperature is lower than 800 ℃, the energy is not enough to produce a p-type zinc oxide thin film is not significant, if higher than 1000 ℃ may cause problems with the sapphire substrate.

Hereinafter, with reference to the accompanying drawings to help the understanding of the present invention will be described in more detail.

1 is a diagram illustrating a source supply sequence per cycle according to an embodiment of the present invention. Referring to FIG. 1 , the order of introduction of Sequence 1 according to the atomic layer deposition method is DEZn-NH ₃ -H ₂ O, and the order of introduction of Sequence ₂ is DEZn-H ₂ O-NH ₃ . .

Figure 2 is a graph showing the electrical characteristics of the ZnO thin film after ammonia doping according to an embodiment of the present invention. This is described in the corresponding part of the embodiment.

3 is a schematic diagram of an atomic model showing the effect of ammonia doping and post-heat treatment according to an embodiment of the present invention. Referring to Figure 3, it is the difference of the sequence 1 and sequence 2 shown in FIG. 1, the change in carrier concentration and the mobility indicates the electric characteristics of the zinc oxide thin film can be described as a model in Fig.

In the case of sequence 1, when NH ₃ is doped after Zn is deposited, it reacts with and adsorbs on -C ₂ H ₅ on the substrate surface as in Scheme 1 below.

NH ₃ + SC ₂ H ₅ → NH ₂ + C ₂ H ₆ ↑

Where S denotes the substrate surface.

In the next step, H ₂ O is supplied and reacts with -C ₂ H ₅ on the substrate surface to produce OH.

H ₂ O + SO-Zn-C ₂ H ₅ → SO-Zn-OH + C ₂ H ₆ ↑

The substrate plot of FIG. 3 depicts oxygen vacancies known to be commonly present in as-grown ZnO thin films, which make the ZnO thin films exhibit n-type properties.

In the next step, DEZn is fed and reacts with -OH on the substrate surface, terminated with -C ₂ H ₅ to complete one cycle and grow a ZnO 1 molecular layer.

Zn (C ₂ H ₅ ) ₂ + S-OH → SO-Zn-C ₂ H ₅ + C ₂ H ₆ ↑

At this time, NH ₂ existing between -OH is changed to NH.

Zn (C ₂ H ₅ ) ₂ + S-NH ₂ → S-NH-Zn-C ₂ H ₅ + C ₂ H ₆ ↑

As such, after one cycle, NH is placed in place of oxygen in a portion of the ZnO wurtzite lattice. NH impurities combined with Zn atoms do not produce holes because nitrogen is passivated by hydrogen. If the heat treatment process is performed in this step, since hydrogen of NH is removed and only nitrogen atoms remain, it acts as an acceptor capable of generating holes. Therefore, the n-type ZnO thin film can be changed to p-type if only the nitrogen concentration in the ZnO thin film is sufficiently high.

NH impurities located in oxygen sites in the ZnO thin film are converted into ionized acceptors by neutral or heat treatment in the as-grown state. In general, carrier mobility is greatly changed by ionized impurities rather than neutral impurities. Therefore, carrier mobility of the ZnO thin film grown in the sequence 1 is reduced by heat treatment.

On the other hand, the model of the second sequence are the two possibilities, as shown in the right side of Fig.

(1) The first possibility is that the doped NH ₃ is separated into nitrogen and oxygen as

NH ₃ → N + 2/3 H ₂ ↑

Nitrogen atoms are neutral invasive atoms that exist in the interstitial site of the lattice and hydrogen is removed. The nitrogen atom already bonds with the zinc atom, making it difficult to replace the oxygen atom and is located in the oxygen vacancies that exist around it. The oxygen vacancies are actually very likely to be far from the invasive nitrogen atoms, so they cannot move to the oxygen vacancies and create holes. Therefore, the ZnO thin film in the as-grown state exhibits the characteristics of the n-type semiconductor, and when sufficient energy is supplied by heat treatment, the nitrogen atoms move to the oxygen vacancy and show the p-type characteristic.

(2) The second possibility is that the doped NH ₃ reacts with -OH on the substrate surface to form an NH ₄ ⁺ -O ^{2 -} bond as shown in the following equation.

^{_{NH 3 + OH - → NH 4}} + -O 2 -

Then, in the DEZn pulse step, the reaction as in Scheme 2 is performed except for the NH ₄ ⁺ site. This NH ₄ ⁺ also has a nitrogen atom immobilized to a hydrogen atom, and thus does not act as an acceptor. Since NH ₄ ⁺ is too large to exist at the zinc position, there is a high possibility that even surrounding Zn—C ₂ H ₅ may not be formed. When the heat treatment is performed in this stage, NH ₄ ⁺ is decomposed and the decomposed nitrogen atoms move to the oxygen vacancies around them to act as p-type acceptors.

_{^{NH 4 + + e - → N}} + 2H 2 ↑

The possibility of (1) and (2) as described above is that the ionized acceptor generates holes through the heat treatment process after the nitrogen impurities move to the oxygen sites. 3 , after the heat treatment, the oxygen vacancies in the substrate still exist in the case of Sequence 1, and are sufficiently reduced in the case of Sequence 2. Due to this difference, the case of Sequence 2 shows higher carrier mobility than that of Sequence 1. The reduction of oxygen vacancies may also occur by heat treatment in an oxygen atmosphere, but the effect on both sequences is likely to be the same.

In conclusion, in order to grow a p-type ZnO thin film in the ALD cycle, NH ₃ doping must be performed immediately before the H 2 O supply step (just after the DEZn supply step). Then, high temperature heat treatment is necessary after that.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are provided to illustrate the best embodiments of the present invention, and of course, the content of the present invention is not limited or limited to only the following examples.

< Example  1> nitrogen Doped  Preparation of Zinc Oxide Thin Film

A zinc oxide thin film doped with sapphire (0001) substrate was grown by ALD method.

NH ₃ was used as the dopant, DEZn (Diethylzinc) and H ₂ O maintained at 10 ° C. in the canister as a source of zinc and oxygen, and the order of injection per cycle was DEZn-NH ₃ -H ₂ O. This is named sequence 1 (see FIG. 1 ). Standard pulse times (pulse time or step time) of DEZn, NH ₃ and H ₂ O were 0.15, 0.05 and 0.2 seconds, respectively, and the cleaning time between each reaction was 2 seconds. The temperature of the substrate was fixed at 150 ° C., and the flow rate of NH ₃ was changed to 1-10 sccm. Sources were sequentially injected and purged with each cycle, and the cycle was repeated 1000 times to grow a ZnO thin film with a target thickness of 3000 mm 3. Thereafter, the ZnO specimen was post-heated at 1000 ° C. in an oxygen atmosphere for 1 hour.

< Example  2> nitrogen Doped  Preparation of Zinc Oxide Thin Film

The order of injection per cycle was called DEZn-H ₂ O-NH ₃ and named as Sequence 2 (see FIG. 1 ). A zinc oxide thin film was manufactured in the same manner as in Example 1 except that the introduction order of the sources was DEZn-H ₂ O-NH ₃ .

< Example  3> nitrogen Doped  Preparation of Zinc Oxide Thin Film

A zinc oxide thin film was prepared in the same manner as in Example 2 except that the pulse time of NH ₃ was 0.1 sec and the flow rate thereof was 10 sccm in Example 2.

Table 1 summarizes the operating conditions of Examples 1 to 3.

Psalter Pulse time (s) NH ₃ flow rate (sccm) Substrate Temperature (℃) Sequence no. DEZn H ₂ O NH ₃ Example 1 0.15 0.2 0.05 3 150 One Example 2 0.15 0.2 0.05 3 150 2 Example 3 0.15 0.2 0.1 10 150 2

< Experimental Example  1> Comparison of Electrical Characteristics

The electrical properties of carrier concentration, carrier mobility and electrical resistivity of the nitrogen doped zinc oxide thin film were measured using a Hall measuring instrument (HEM-2000) and the results are shown in FIG. 2 . All three specimens according to Examples 1 to 3 exhibited n-type characteristics in the as-grown state, and then showed p-type characteristics after oxygen heat treatment at 1000 ° C. The specimen of Sequence 2 had a much higher change in carrier concentration due to heat treatment than the specimen of Sequence 1. As described above, the lowest resistivity of the p-type ZnO thin film produced by the ALD method was 17.9 Ωcm, and the hole concentration was 1.59 × 10 ¹⁷ cm ³ .

As a result, when the ammonia flow rate was applied at 3 sccm, the specimen of Sequence 2 showed a higher n-type carrier concentration in the as-grown state and a higher p-type carrier concentration after heat treatment. The heat-treated ZnO specimens showed higher p-type carrier concentration and lower mobility when 10 sccm was applied compared to 3 sccm of ammonia flow rate. The carrier mobility change by heat treatment decreased in the case of Sequence 1 but increased in the case of Sequence 2.

Carrier concentration and mobility depended heavily on the pulse time and injection sequence of NH ₃ . Carrier mobility was high in the as-grown when the ALD process proceeded to Sequence 1 but decreased after the heat treatment, and decreased after the heat treatment when proceeded to the Sequence 2, but increased after the heat treatment. Both sequences 1 and 2 exhibited n-type characteristics in as-grown state, but were converted to p-type after annealing. In sequence 2, carrier concentration increased more than sequence 1 after annealing.

Implementation of a high quality zinc oxide semiconductor thin film having excellent optical, structural and electrical properties according to the present invention provides a high quality zinc oxide thin film which is a basic step for mass production of light emitting diodes and laser diodes using zinc oxide oxide semiconductors. Commercialization for mass production of oxide semiconductors can be accelerated. In addition, by implementing a p-type zinc oxide thin film excellent in the optical and electrical properties due to the post-heat treatment process it is possible to improve the light emitting device characteristics. In addition, it is possible to reduce the defects present in the zinc oxide has the effect of increasing the efficiency of the light emitting device.

Claims (14)

a) supplying a zinc source to deposit zinc containing species on the substrate; b) supplying an oxygen source to deposit an oxygen containing species on the substrate on which the zinc containing species are deposited; c) supplying a nitrogen source as a dopant source to dope the nitrogen containing species onto the substrate on which the oxygen containing species are deposited; And d) A method of manufacturing a p-type zinc oxide thin film by an atomic layer deposition method comprising the step of post-heat treatment in an oxygen atmosphere to produce a hole. a ') supplying a zinc source to the reactor to deposit zinc containing species on the substrate; b ') a first purification step of removing unreacted zinc sources and reaction byproducts; c ') supplying an oxygen source to deposit an oxygen containing species on the substrate on which the zinc containing species are deposited; d ') a second purge step of removing unreacted oxygen sources and reaction byproducts; e ') supplying a nitrogen source as a dopant source to dope the nitrogen containing species onto the substrate on which the oxygen containing species are deposited; And f ') A method for producing a p-type zinc oxide thin film by atomic layer deposition, comprising a third purifying step of removing unreacted nitrogen sources and reaction by-products. a ") supplying a zinc source to deposit zinc containing species on the substrate; b ") a first purification step to remove unreacted zinc sources and reaction byproducts; c ") supplying a nitrogen source as a dopant source to dope the nitrogen containing species onto the substrate on which the zinc containing species are deposited; d ") a second purge step of removing unreacted nitrogen sources and reaction byproducts; e ″) supplying an oxygen source to deposit oxygen containing species on the nitrogen doped substrate; and f ") A method for producing a p-type zinc oxide thin film by atomic layer deposition, comprising a third purifying step of removing unreacted oxygen sources and reaction by-products. The method of manufacturing a p-type zinc oxide thin film according to claim 1, wherein the cycle is repeated until a zinc oxide film having a target thickness is formed using the steps a) to c) as one cycle. The method for producing a p-type zinc oxide thin film according to claim 1, wherein the zinc source is dimethyl zinc. The method for producing a p-type zinc oxide thin film according to claim 1, wherein the oxygen source is water of high purity or oxygen gas. The method of manufacturing a p-type zinc oxide thin film according to claim 1, wherein the dopant source is ammonia. The method of claim 1, wherein the zinc source, oxygen source and dopant source are dimethylzinc, high purity water and ammonia, respectively. The method of claim 1, wherein the substrate is a sapphire, silicon or glass substrate. The method of claim 1, wherein the temperature of the substrate is maintained at 150 ° C to 180 ° C. The atomic layer of claim 1, wherein step a) lasts for 0.1-0.2 seconds per cycle, step b) lasts for 0.1-0.3 seconds per cycle, and step c) lasts for 0.01-0.1 seconds per cycle. A method for producing a p-type zinc oxide thin film by vapor deposition. The method of claim 2 or 3, wherein the purifying step is performed by vacuum purifying or by supplying an inert gas to purify the p-type zinc oxide thin film by the atomic layer deposition method. The method of claim 1, wherein the post-heat treatment step is performed for 1 to 3 hours under an oxygen atmosphere of 800 ° C to 1,000 ° C. The method for producing a p-type zinc oxide thin film according to claim 13, wherein the oxygen atmosphere temperature is 1000 ° C.

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